• Title/Summary/Keyword: Redox mechanism

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Peroxiredoxins and the Regulation of Cell Death

  • Hampton, Mark B.;O'Connor, Karina M.
    • Molecules and Cells
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    • v.39 no.1
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    • pp.72-76
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    • 2016
  • Cell death pathways such as apoptosis can be activated in response to oxidative stress, enabling the disposal of damaged cells. In contrast, controlled intracellular redox events are proposed to be a significant event during apoptosis signaling, regardless of the initiating stimulus. In this scenario oxidants act as second messengers, mediating the post-translational modification of specific regulatory proteins. The exact mechanism of this signaling is unclear, but increased understanding offers the potential to promote or inhibit apoptosis through modulating the redox environment of cells. Peroxiredoxins are thiol peroxidases that remove hydroperoxides, and are also emerging as important players in cellular redox signaling. This review discusses the potential role of peroxiredoxins in the regulation of apoptosis, and also their ability to act as biomarkers of redox changes during the initiation and progression of cell death.

The photocatalytic water splitting into $H_2$ and $O_2$ mimicking a Z-scheme mechanism (광합성을 모사한 광촉매 물분해 수소 제조)

  • Jeon, Myung-Seok;Hong, Joon-Gi;Chun, Young-Gab;Choi, Ho-Suk
    • Journal of the Korean Solar Energy Society
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    • v.23 no.4
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    • pp.29-35
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    • 2003
  • We studied the water splitting into $H_2$ and $O_2$ using two different semiconductor photo catalysts and redox mediator, mimicking the Z-scheme mechanism of the photosynthesis, $H_2$ evolution took place on a Pt-$SrTiO_2$ (Cr-Ta doped) photocatalyst using $I^-$ electron donor under the visible light irradiation. The Pt-$WO_3$ photocatalyst showed an excellent activity of the $O_2$ evolution using $IO_3^-$ electron acceptor under visible light. $H_2$ and $O_2$ gases evolved in the stoichiometric ratio($H_2/O_2$=2) under visible light using a mixture of the Pt-$WO_3$ and Pt-$SrTiO_3$ (Cr-Ta doped) suspended in NaI aqueous solution. We proposed a two-step photo-excitation mechanism using redox mediator under the visible irradiation.

Reset-first Resistance Switching Mechanism of HfO2 Films Based on Redox Reaction with Oxygen Drift-Diffusion

  • Kim, Jong-Gi;Lee, Sung-Hoon;Lee, Kyu-Min;Na, Hee-Do;Kim, Young-Jae;Ko, Dae-Hong;Sohn, Hyun-Chul
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.286-287
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    • 2012
  • Reset-first resistive switching mechanism based on reduction reaction in HfO2-x with oxygen drift-diffusion was studied. we first report that the indirect evidence of local filamentary conductive path formation in bulk HfO2 film with local TiOx region at Ti top electrode formed during forming process and presence of anion-migration at interface between electrode and HfO2 during resistive switching through high resolution transmission electron microscopy (HRTEM), electron disperse x-ray (EDX), and electron energy loss spectroscopy (EELS) mapping. Based on forming process mechanism, we expected that redox reaction from Ti/HfO2 to TiOx/HfO2-x was responsible for an increase of initial current with increasing the post-annealing process. First-reset resistive switching in above $350^{\circ}C$ annealed Ti/HfO2 film was exhibited and the redox phenomenon from Ti/HfO2 to TiOx/HfO2-x was observed with high angle annular dark field (HAADF) - scanning transmission electron microscopy (STEM), EDX and x-ray photoelectron spectroscopy. Therefore, we demonstrated that the migration of oxygen ions at interface region under external electrical bias contributed to bipolar resistive switching behavior.

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Kinetics and Mechanism for Redox Reaction of cis-$[Co(en)_2(N_3)_2]^+$ with Fe(II) in Acidic Solution (산 촉매하에서 cis-$[Co(en)_2(N_3)_2]^+$ 와 Fe(II) 와의 산화-환원반응에 대한 반응속도와 메카니즘)

  • Byung-Kak Park;Kwang-Jin Kim;Joo-Sang Lim
    • Journal of the Korean Chemical Society
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    • v.33 no.3
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    • pp.309-314
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    • 1989
  • A kinetic study was carried out for the redox reaction of cis-$[Co(en)_2(N_3)_2]^+$ with Fe(II) in acidic solution by spectrophotometric methods. This redox reaction system have been found to show a third order for overall reaction as the respective first order with respect to reactant cis-$[Co(en)_2(N_3)_2]^+$, Fe(II), and $H^+$ catalyst. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were obtained as 14.2Kcal/mol and -16.7 e.u., respectively. On the basis of the kinetic data, we suggest that the redox reaction system proceeds via inner sphere mechanism. The rate equation derived from the proposed mechanism is in agreement with the observed rate equation.

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Study of the Electrochemical Redox Characteristics of Some Triazolopyrimidines

  • Maghraby, A.A. El;Elenien, G.M. Abou;Shehata, K.I.
    • Journal of the Korean Electrochemical Society
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    • v.10 no.3
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    • pp.159-168
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    • 2007
  • An electrochemical study related to the redox characteristics of Ethyl-3-acetyl-6-methyl-1, 4-diphenyl-4, 3a-dihydro-1, 3, 4-triazolino[3, 4-a] pyrimidine-5-carboxylate ester and its derivatives (1a-f) and (2a-e) in nonaqueous solvents such as 1, 2-dichloroethane (DCE), dichloromethane (DCM), acetonitrile (AN), dimethylsulphoxide (DMSO) and tetrahydrofurane (THF) using $0.1\;mol\;dm^{-3}$ tetrabutylammonium perchlorate (TBAP) as a supporting electrolyte at platinum, glassy carbon and gold electrodes, has been performed using cyclic voltammetry (CV). Controlled potential electrolysis (CPE) is also carried out to elucidate the course of different electrochemical reactions through the separation and identification of the intermediates and final electrolysis products. The redox mechanism is suggested and proved. It was found that all the investigated compounds in all solvents are oxidized in a single irreversible one electron donating process following the well known pattern of the EC-mechanism to give a dimer. On the other hand, these compounds are reduced in a single irreversible one electron step to form the anion radical, which is basic enough to proton from the media forming the radical which undergoes tautomerization and then dimerization processes to give also another bis-compound through N-N linkage formation.

Corrosion and Passivation of Copper in Artificial Sea Water (인공해수에서 구리의 부식과 부동화 반응)

  • Chon, Jung-Kyoon;Kim, Youn-Kyoo
    • Journal of the Korean Chemical Society
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    • v.51 no.4
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    • pp.305-311
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    • 2007
  • Based on the cyclic voltammograms, potentiodynamic polarizations, transient and steady state Tafel plots and electrochemical impedence spectroscopy, we proposed the copper redox mechanism of the corrosion and passivation in artificial sea water. The copper redox mechanism showed the dependence of the concentration of oxygen in artificial sea water and electrode potentials.

A Study on the Treatment of Heavy Metal in Wastewater by Redox Reaction of Cu-Zn Metal Alloy and Adsorption reaction of Al-Silicate (Cu-Zn 금속합금의 산화 환원반응과 Al-Silicate의 흡착반응을 이용한 폐수 중 중금속처리에 관한 연구)

  • Lee, Soo-Jeong;Kim, Jong Hwa;Song, Ju Yeong
    • Journal of the Korean Applied Science and Technology
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    • v.33 no.3
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    • pp.441-448
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    • 2016
  • Heavy metal removal study is conducted from synthetic waste water by reduction and oxidation(redox) reaction of Cu-Zn metal alloy and adsorption reaction of aluminium silicate. Heavy metal whose ionization tendency is smaller than zinc are reducted in an aqueous solution, and the concentration of ionized zinc is reduced by adsorption reaction. The average diameter of metal alloy micro fiber is about $200{\mu}m$, and the surface area is wide enough to get equilibrium in a single cycle treatment. A single cycle treatment of redox reaction of Cu-Zn metal alloy, could remove 100.0 % of Cr(III), 98.0 % of Hg, 92.0 % of Sn and 91.4 % of Cu respectively. An ionization tendency of chromium is very close to zinc, but removal efficiency of chromium by redox reaction is significant. This result shows that trivalent chromium ion is expected to generate hydroxide precipitation with $OH^-$ ion generated by redox reaction. Zinc ion generated by redox reaction is readily removed by adsorption reaction of aluminium silicate in a single cycle treatment. Other heavy metal components which are not perfectly removed by redox reaction also showed very high removal efficiency of 98.0 % or more by adsorption reaction. Aluminium ion is not increased by adsorption reaction of aluminium silicate. That means heavy metal ion removal mechanism by adsorption reaction is turned out to be not an ion exchange reaction, but an adsorption reaction.

Voltammetric Studies on Some Thiadiazoles and Their Derivatives

  • Maghraby, A. A. El;Abou-Elenien, G. M.;Rateb, N. M;Abdel-Tawab, H. R.
    • Journal of the Korean Electrochemical Society
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    • v.12 no.1
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    • pp.54-60
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    • 2009
  • The redox characteristics of 2-arylaldehydehydrazono-3-phenyl-5-substituted-2, 3-dihydro-1, 3, 4-thiadiazoles (1a-h) have been investigated in nonaqueous solvents such as 1, 2-dichloroethane (DCE), dichloromethane (DCM), acetonitrile (AN), Tetrahydrofuran (THF), and dimethylsulfoxide (DMSO) at platinum electrode. Through controlled potential electrolysis, the oxidation and reduction products of the investigated compounds had been separated and indentified. The redox mechanism had been suggested and proved. It had been found that all the investigated compounds were oxidized in two irreversible one-electron processes following the well-known pattern of The EC-mechanism; the first electron loss gives the corresponding cation-radical which is followed by proton removal from the ortho-position in the N-phenyl ring forming the radical. The obtained radical undergoes a second electron uptake from the nitrogen in the N = C group forming the unstable intermediate (di-radical cation) which undergoes ring closure forming the corresponding cation. The formed cation was stabilized in solution through its combination with a perchlorate anion from the medium. On the other hand, these compounds are reduced in a single two-electron process or in a successive two one-electron processes following the well known pattern of the EEC-mechanism according to the nature of the substituent; the first one gives the anion-radical followed by a second electron reduction to give the dianion which is basic enough to abstract protons from the media to saturate the (C = O) bond.

Growth-Dependent Variations in Antioxidant and Redox Enzyme Activities of Schizosaccharomyces pombe

  • Cho, Young-Wook;Park, Eun-Hee;Ahn, Ki-Sup;Kim, Dae-Myung;Lim, Chang-Jin
    • BMB Reports
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    • v.34 no.3
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    • pp.278-283
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    • 2001
  • Antioxidant and redox enzyme activities are known to be involved in the cellular responses to various stresses. Their variations were observed according to the growth cycle of the fission yeast Schizosaccharomyces pombe. Peroxidase activity appeared to be notably higher in the early exponential phase than in the mid-exponential and stationary phases. However, catalase activity showed a variation pattern resembling the growth curve. Glutathione S-transferase activity was higher in the early exponential and late stationary phases. Activities of the two redox enzymes, thioredoxin and thioltransferase (glutaredoxin), were high in the stationary phase. However, their activities appeared to increase from the early exponential to mid-exponential phase. Total glutathione content had a varying pattern similar to that of thioredoxin and thioltransferase. However, its content in the early exponential phase was high. These results propose that antioxidant and redox enzymes tested are also involved in the mechanism of cell growth.

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Thiol-dependent Redox Mechanisms in the Modification of ATP-Sensitive Potassium Channels in Rabbit Ventricular Myocytes

  • Han, Jin;Kim, Na-Ri;Cuong, Dang-Van;Kim, Chung-Hui;Kim, Eui-Yong
    • The Korean Journal of Physiology and Pharmacology
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    • v.7 no.1
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    • pp.15-23
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    • 2003
  • Cellular redox state is known to be perturbed during ischemia and that $Ca^{2+}$ and $K^2$ channels have been shown to have functional thiol groups. In this study, the properties of thiol redox modulation of the ATP-sensitive $K^2$ ($K_{ATP}$) channel were examined in rabbit ventricular myocytes. Rabbit ventricular myocytes were isolated using a Langendorff column for coronary perfusion and collagenase. Single-channel currents were measured in excised membrane patch configuration of patch-clamp technique. The thiol oxidizing agent 5,5'-dithio-bis-(2-nitro-benzoic acid) (DTNB) inhibited the channel activity, and the inhibitory effect of DTNB was reversed by dithiothreitol (disulfide reducing agent; DTT). DTT itself did not have any effect on the channel activity. However, in the patches excised from the metabolically compromised cells, DTT increased the channel activity. DTT had no effect on the inhibitory action by ATP, showing that thiol oxidation was not involved in the blocking mechanism of ATP. There were no statistical difference in the single channel conductance for the oxidized and reduced states of the channel. Analysis of the open and closed time distributions showed that DTNB had no effect on open and closed time distributions shorter than 4 ms. On the other hand, DTNB decreased the life time of bursts and increased the interburst interval. N-ethylmaleimide (NEM), a substance that reacts with thiol groups of cystein residues in proteins, induced irreversible closure of the channel. The thiol oxidizing agents (DTNB, NEM) inhibited of the $K_{ATP}$ channel only, when added to the cytoplasmic side. The results suggested that metabolism-induced changes in the thiol redox can also modulate $K_{ATP}$ channel activity and that a modulatory site of thiol redox may be located on the cytoplasmic side of the $K_{ATP}$ channel in rabbit ventricular myocytes.